CN113881403A - Composite phase change material and preparation method and application thereof - Google Patents
Composite phase change material and preparation method and application thereof Download PDFInfo
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- CN113881403A CN113881403A CN202111066831.5A CN202111066831A CN113881403A CN 113881403 A CN113881403 A CN 113881403A CN 202111066831 A CN202111066831 A CN 202111066831A CN 113881403 A CN113881403 A CN 113881403A
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Abstract
The invention discloses a composite phase-change material and a preparation method and application thereof. The composite phase change material comprises the following components in parts by mass: mannitol: 75-95 parts; inorganic potassium salt: 5-25 parts; expanded graphite: 5-15 parts; the total amount of mannitol and inorganic potassium salt is 100 parts. The preparation method of the composite phase-change material comprises the following steps: 1) mixing inorganic potassium salt and mannitol, and heating to completely melt to obtain a molten mixture; 2) and adding the expanded graphite into the molten mixture, and standing in vacuum to obtain the composite phase-change material. The phase change temperature of the composite phase change material is 130-146 ℃, the blank of the temperature region of the existing phase change material at 100-150 ℃ is made up, the application range is widened, the stability is good, the phase change enthalpy value is high, the heat conductivity is higher, the preparation process is simple, and the composite phase change material can be used in the fields of medium-temperature heat storage, industrial waste heat recovery and the like.
Description
Technical Field
The invention relates to the technical field of phase change energy storage materials, in particular to a composite phase change material and a preparation method and application thereof.
Background
With the rapid development of economy, the problems of energy crisis and environmental pollution are highlighted, low carbon and energy conservation are development trends, and in order to achieve the aims of carbon peak reaching and carbon neutralization, the fundamental point of solving the problems is to reduce carbon emission from the source and develop renewable energy. The solar energy has the advantages of wide source, no need of mining, cleanness, environmental friendliness and the like, is a renewable energy source with very wide application prospect, and can greatly reduce the dependence of people on fossil energy by efficiently utilizing the renewable energy source. However, the utilization of solar energy often has a contradiction between supply and demand in time and space, and the development and application of the phase change energy storage technology can effectively solve the problem and improve the utilization efficiency of solar energy. At present, most of phase change materials researched are low-temperature phase change materials, the application range of the phase change materials is limited, and the phase change materials suitable for medium-temperature heat storage only contain sugar alcohol, a small part of hydrate, chloride and the like, and cannot meet the actual application requirements of medium-temperature heat storage.
Therefore, it is highly desirable to develop a phase change material with high enthalpy of phase change and high thermal conductivity, which is suitable for medium-temperature heat storage.
Disclosure of Invention
The invention aims to provide a composite phase change material and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
the composite phase change material comprises the following components in parts by mass:
mannitol: 75-95 parts;
inorganic potassium salt: 5-25 parts;
expanded graphite: 5-15 parts;
the total amount of mannitol and inorganic potassium salt is 100 parts.
Preferably, the composite phase change material comprises the following components in parts by mass:
mannitol: 80-90 parts of a stabilizer;
inorganic potassium salt: 10-20 parts;
expanded graphite: 5-15 parts;
the total amount of mannitol and inorganic potassium salt is 100 parts.
Preferably, the inorganic potassium salt is KBr, KCl, KNO3At least one of (1).
Preferably, the particle size of the expanded graphite is less than or equal to 250 mu m, and the expansion rate is more than or equal to 99 percent.
The preparation method of the composite phase-change material comprises the following steps:
1) mixing inorganic potassium salt and mannitol, and heating to completely melt to obtain a molten mixture;
2) and adding the expanded graphite into the molten mixture, and standing in vacuum to obtain the composite phase-change material.
Preferably, the heating in the step 1) is carried out at 150-170 ℃, and the heating time is 1-2 h.
Preferably, magnetic stirring is performed during the heating in step 1).
Preferably, the vacuum standing in the step 2) is carried out at the temperature of 150-170 ℃, and the standing time is 4-7 h.
Preferably, the vacuum standing process in the step 2) is intermittently stirred, and the stirring is stopped for 1 to 2 hours after every 5 to 10 minutes of stirring.
The invention has the beneficial effects that: the phase change temperature of the composite phase change material is 130-146 ℃, the blank of the temperature region of the existing phase change material at 100-150 ℃ is made up, the application range is widened, the stability is good, the phase change enthalpy value is high, the heat conductivity is higher, the preparation process is simple, and the composite phase change material can be used in the fields of medium-temperature heat storage, industrial waste heat recovery and the like.
Specifically, the method comprises the following steps:
1) the phase transition temperature of the composite phase change material is 130-146 ℃ and is lower than the phase transition temperature of mannitol 162-166 ℃, the blank of the temperature region of the existing phase change material at 100-150 ℃ is made up, and the application range is widened;
2) the heat conductivity coefficient of the composite phase change material can reach 7.7W/(m.K) which is far higher than 0.6W/(m.K) of mannitol;
3) the photothermal conversion rate of the composite phase change material can reach 42.7 percent, which is far higher than 27.4 percent of mannitol, and the utilization rate of solar energy is improved;
4) the composite phase-change material is added with the heat-conducting matrix expanded graphite, so that the heat conductivity of the phase-change material can be improved, the leakage problem of the phase-change material in the solid-liquid conversion process can be solved, the light energy conversion performance of the phase-change material can be improved, and the utilization rate of solar energy can be improved;
5) the preparation method of the composite phase-change material is simple, the preparation conditions are mild, and the composite phase-change material is suitable for large-scale industrial production.
Drawings
FIG. 1 is a differential scanning calorimetry plot of the composite phase change material of example 1 and a potassium bromide-mannitol eutectic material.
Fig. 2 is an SEM image of the composite phase change material and expanded graphite of example 1.
FIG. 3 is a TGA curve of the composite phase change material of example 1 and a potassium bromide-mannitol eutectic material.
FIG. 4 is a graph of the temperature change with time of the composite phase change material and the potassium bromide-mannitol eutectic material of example 1 under simulated sunlight.
FIG. 5 is a graph showing the results of the thermal conductivity test of the composite phase change material of example 1.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a preparation method of the composite phase-change material comprises the following steps:
1) mixing 20g of potassium bromide (KBr) and 80g of mannitol (Man), heating to 160 ℃, and magnetically stirring for 2 hours to obtain a molten mixture;
2) and adding 10g of expanded graphite with the particle size of 200 mu m and the expansion rate of 99% into the molten mixture, standing for 7 hours in a vacuum box at 160 ℃, intermittently stirring in the standing process, and stopping stirring for 1 hour after stirring for 10min to obtain the composite phase-change material.
And (3) performance testing:
1) the differential scanning calorimetry of the composite phase change material (denoted as EG/KBr-Man) and the potassium bromide-mannitol eutectic material (composed of potassium bromide and mannitol in a mass ratio of 1:9, denoted as EG/Man) of this example is shown in fig. 1.
As can be seen from fig. 1: the phase change temperature of the composite phase change material of the embodiment is 146 ℃, the latent heat of phase change is 220J/g, while the phase change temperature of the potassium bromide-mannitol eutectic material is 142.87 ℃, and the latent heat of phase change is 234.5J/g.
2) The Scanning Electron Microscope (SEM) images of the composite phase change material and the expanded graphite of the present example are shown in fig. 2(a is the expanded graphite, and b is the composite phase change material).
As can be seen from fig. 2: the expanded graphite is in a porous sheet laminated structure, obvious gaps can be seen, and the inter-sheet layers of the expanded graphite are filled with the phase-change material after the expanded graphite absorbs the eutectic phase-change material.
3) The thermal weight loss (TGA) curves of the composite phase change material (denoted as EG/KBr-Man) and the potassium bromide-mannitol eutectic material (composed of potassium bromide and mannitol in a mass ratio of 1:9, denoted as EG/Man) of the present example are shown in fig. 3.
As can be seen from fig. 3: the composite phase-change material and the potassium bromide-mannitol eutectic material start weight loss at about 260 ℃, decomposition is completed at about 360 ℃, the residue after the decomposition of the potassium bromide-mannitol eutectic material is potassium bromide, the mass ratio is about 22%, the mass ratio is close to the addition ratio of the potassium bromide in the potassium bromide-mannitol eutectic material, the residue after the decomposition of the composite phase-change material is potassium bromide and expanded graphite, the mass ratio is about 30%, and the mass ratio is basically consistent with the addition ratio of the raw materials.
4) The composite phase change material (marked as EG/KBr-Man) and the potassium bromide-mannitol eutectic material (composed of potassium bromide and mannitol in a mass ratio of 1:9, marked as EG/Man) of this example were used as test samples, irradiation was performed with AM1.5 simulated sunlight, the change in temperature of the samples with irradiation time was measured with a thermocouple, the resulting temperature change curve with time under simulated sunlight was shown in fig. 4, and the photothermal conversion rate of the samples was calculated by the following formula:
η＝m(ΔH+Q)/P·S·Δt，
in the formula, m is the mass of the sample, Δ H is the phase change enthalpy of the sample, Q is the sensible heat of the sample, P is the illumination intensity of the simulated sunlight, S is the area of the sample, and Δ t is the irradiation time.
As can be seen from fig. 4: the light conversion rate of the composite phase change material of the embodiment under simulated sunlight is 42.7%, and the light conversion rate of the potassium bromide-mannitol eutectic material is 27.4%.
5) A graph of the thermal conductivity test results of the composite phase change material of the present embodiment is shown in fig. 5.
As can be seen from fig. 5: the thermal conductivity of the composite phase change material of the present example was 4.9W/(m.K), 5.4W/(m.K) and 7.7W/(m.K) at pressures of 10kN, 20kN and 30kN, respectively.
Example 2:
a preparation method of the composite phase-change material comprises the following steps:
1) mixing 10g of potassium bromide and 90g of mannitol, heating to 170 ℃, and magnetically stirring for 2 hours to obtain a molten mixture;
2) and adding 10g of Expanded Graphite (EG) with the particle size of 200 mu m and the expansion rate of 99% into the molten mixture, standing for 6 hours in a vacuum box at 170 ℃, intermittently stirring in the standing process, and stopping stirring for 1 hour after stirring for 5min to obtain the composite phase-change material.
Through tests, the phase change temperature of the composite phase change material is 142 ℃, the phase change latent heat is 197J/g, and the light conversion rate under simulated sunlight is 33.2%.
Example 3:
a preparation method of the composite phase-change material comprises the following steps:
1) mixing 20g of potassium bromide and 80g of mannitol, heating to 160 ℃, and magnetically stirring for 2 hours to obtain a molten mixture;
2) adding 15g of expanded graphite with the particle size of 220 mu m and the expansion rate of 99% into the molten mixture, standing for 5h at 155 ℃ in a vacuum box, stirring intermittently during the standing process, and stopping stirring for 1h after stirring for 10min to obtain the composite phase-change material.
Through tests, the phase change temperature of the composite phase change material is 138 ℃, the phase change latent heat is 186J/g, and the light conversion rate under simulated sunlight is 42.0%.
Example 4:
a preparation method of the composite phase-change material comprises the following steps:
1) mixing 15g of potassium chloride and 85g of mannitol, heating to 165 ℃, and magnetically stirring for 2 hours to obtain a molten mixture;
2) and adding 10g of expanded graphite with the particle size of 240 mu m and the expansion rate of 99% into the molten mixture, standing for 5.5 hours in a vacuum box at 165 ℃, intermittently stirring in the standing process, and stopping stirring for 1 hour after every 7 minutes of stirring to obtain the composite phase-change material.
Through tests, the phase change temperature of the composite phase change material is 134 ℃, the phase change latent heat is 180J/g, and the light conversion rate under simulated sunlight is 38.2%.
Example 5:
a preparation method of the composite phase-change material comprises the following steps:
1) mixing 15g of potassium chloride and 85g of mannitol, heating to 150 ℃, and magnetically stirring for 2 hours to obtain a molten mixture;
2) and adding 10g of expanded graphite with the particle size of 180 mu m and the expansion rate of 99% into the molten mixture, standing for 6h in a vacuum box at 150 ℃, intermittently stirring in the standing process, and stopping stirring for 1h after stirring for 5min to obtain the composite phase-change material.
Through tests, the phase change temperature of the composite phase change material is 132 ℃, the phase change latent heat is 170J/g, and the light conversion rate under simulated sunlight is 38.0%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The composite phase change material is characterized by comprising the following components in parts by mass:
mannitol: 75-95 parts;
inorganic potassium salt: 5-25 parts;
expanded graphite: 5-15 parts;
the total amount of mannitol and inorganic potassium salt is 100 parts.
2. The composite phase change material according to claim 1, characterized by comprising the following components in parts by mass:
mannitol: 80-90 parts of a stabilizer;
inorganic potassium salt: 10-20 parts;
expanded graphite: 5-15 parts;
the total amount of mannitol and inorganic potassium salt is 100 parts.
3. The composite phase change material according to claim 1 or 2, characterized in that: the inorganic sylvite is KBr, KCl or KNO3At least one of (1).
4. The composite phase change material according to claim 1 or 2, characterized in that: the particle size of the expanded graphite is less than or equal to 250 mu m, and the expansion rate is more than or equal to 99 percent.
5. The preparation method of the composite phase change material as claimed in any one of claims 1 to 4, characterized by comprising the following steps:
1) mixing inorganic potassium salt and mannitol, and heating to completely melt to obtain a molten mixture;
2) and adding the expanded graphite into the molten mixture, and standing in vacuum to obtain the composite phase-change material.
6. The method for preparing the composite phase-change material according to claim 5, wherein: the heating in the step 1) is carried out at the temperature of 150-170 ℃, and the heating time is 1-2 h.
7. The method for preparing the composite phase change material according to claim 5 or 6, wherein: and (2) performing magnetic stirring in the heating process of the step 1).
8. The method for preparing the composite phase-change material according to claim 5, wherein: and 2) carrying out vacuum standing at the temperature of 150-170 ℃, wherein the standing time is 4-7 h.
9. The method for preparing a composite phase change material according to any one of claims 5, 6 and 8, wherein: and 2) carrying out intermittent stirring in the vacuum standing process, and stopping stirring for 1-2 h after stirring for 5-10 min.
10. Use of the composite phase change material according to any one of claims 1 to 4 in heat storage or industrial waste heat recovery.
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